Photosensitive bis(halomethyloxadiazole) compound and photosensitive transfer sheet using the same

ABSTRACT

Photosensitive bis (halomethyloxadiazole) compounds which are capable of producing free radicals upon exposure to light represented by the following general formulae (1) to (4): ##STR1## The symbols in the above formulae are defined in the present specification. The photosensitive bis(halomethyloxadiazole) compound is useful in the fields of recording materials such as photosensitive protecting films, printing plates, photoresists, proofs, etc. Furthermore, a photosensitive transfer sheet using a photosensitive composition containing the photosensitive bis(halomethyloxadiazole) is useful in making a prepress proof for color proofing, a color display, etc.

FIELD OF THE INVENTION

The present invention relates to a novel photosensitivebis(halomethyloxadiazole) compound capable of producing free radicalsupon exposure to light. The photosensitive bis(halomethyloxadiazole)compound is useful in the fields of recording materials such asphotosensitive protecting films, printing plates, photoresists, proofs,etc. Furthermore, the present invention relates to a photosensitivetransfer sheet for use in making a prepress proof for color proofing, acolor display or the like.

BACKGROUND OF THE INVENTION

Compounds capable of forming free radicals by photolysis upon exposureto light (free radical forming agent) are well known in the fields ofgraphic arts and photosensitive recording materials. Such compounds arewidely used as a photoradical polymerization initiator in aphotopolymerizable composition, as a photoactivator in a free radicalphotographic composition, and as a photoinitiator in reactions in whichan acid produced by exposure to light catalyze. Various photosensitivematerials useful in recording systems such as printing, reproduction,duplication and so on, are prepared using the free radical generatingagents.

Bis(trihalomethyl)-s-triazine compounds are proposed as halogen freeradical generating agents which are sensitive to light of wavelengthsranging from near ultraviolet to visible region. Such compounds aredescribed in detail, e.g., in U.S. Pat. Nos. 3,954,475, 3,987,037 and4,189,323, and JP-A-62-58241 (the term "JP-A"as used herein means an"unexamined published Japanese patent application"). Although thosecompounds are sensitive to light having a wavelength of from nearultraviolet to visible region, they have a problem that theirdecomposition products upon exposure tend to generate a pale yellowstain, and further, in such a system that a photoradical polymerizationinitiator or decomposition products thereof remain in a recording layer,a yellow stain due to photolysis generates upon storage under daylight.These phenomena are severe problems in the field such as a color proof,in which a minute change of color tone makes a defect.

As a result of our intensive studies on the above described problems,the inventors have found compounds having excellent properties.

SUMMARY OF THE INVENTION

An object of the present invention is to provide photosensitivebis(halomethyloxadiazole) compounds which are sensitive to light havinga wavelength of from near ultraviolet to visible region, with thesensitivities being high, and generate no color stain due to thedecomposition upon exposure and during storage under daylight.

Another object of the present invention is to provide a photosensitivetransfer sheet using the photosensitive bis(halomethyloxadiazole)compounds which generates no color stain.

The above objects of the present invention is achieved by providing:

photosensitive bis(halomethyloxadiazole) compounds represented by one ofthe following general formulae (1) to (4): ##STR2## wherein R¹represents --CO--R⁶ --CO--, --C_(n) H_(2n) --, or --C_(n) H_(2n) --R⁷--C_(n) H_(2n) --; n represents an integer of from 1 to 20; R², R³, R¹²and R¹³ are the same or different, and each represents a hydrogen atom,an alkyl group containing 1 to 10 carbon atoms, an alkoxy groupcontaining 1 to 10 carbon atoms, an acyloxy group containing 2 to 10carbon atoms, or a halogen atom; R⁴, R⁵, R¹⁴ and R¹⁵ are the same ordifferent, and each represents a hydrogen atom, an alkyl groupcontaining 1 to 10 carbon atoms, an unsubstituted phenyl group, or asubstituted phenyl group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; X, Y and Z are thesame or different, and each represents a hydrogen atom or a halogenatom, providing that all of X, Y and Z cannot be hydrogen atomssimultaneously; R⁶ represents --C_(m) H_(2m) -- or --OC_(m) H_(2m) O--;m represents an integer of from 2 to 20; R⁷ represents --O--, --S--,--N(R⁸)--, --SO₂ --, --O--SO--O--, --O--CO--R⁹ --CO--O--, --SO₂ --R⁹--SO₂ --, --CO--R⁹ --CO--, or --O--R¹⁰ --O--; R⁸ represents an alkylgroup containing 1 to 10 carbon atom, an unsubstituted phenyl group, ora substituted phenyl group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; R⁹ represents --C₁ H₂₁--, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --, --NHC_(k) H_(2k) NH--, --NHC_(k-2)H_(2k) NH--, --NHCH₂ --C₆ H₄ --CH₂ NH--, --OC_(k) H_(2k) O--, or --C₆ H₄--; 1 represents an integer of from 1 to 20; k represents an integer offrom 2 to 20; R¹⁰ represents --C_(p) H_(2p) -- or --C_(p) H_(2p)--O--R¹¹ --OC_(p) H_(2p) --; p represents an integer of from 2 to 20;R¹¹ represents --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, --C₆ H₄ --S--C₆ H₄ --,--C₆ H₄ --SO₂ --C₆ H₄ --, --C₆ H₄ --, --C₆ H₄ --O--C₆ H₄ --, --C₆ H₄--C(CF₃)₂ --C₆ H₄ -- or --C₆ H₄ --C₆ H₄ --; and q represents an integerof from 2 to 10; and

a photosensitive transfer sheet comprising a support having thereon (a)a peeling layer containing an organic polymer and (b) aphotopolymerizable photosensitive resin layer containing aphotosensitive resin and a photopolymerization initiator, in this order,wherein the photopolymerization initiator comprises at least onephotosensitive bis(halomethyloxadiazole) compound represented by one ofthe foregoing general formulae (1) to (4).

DETAILED DESCRIPTION OF THE INVENTION

The photosensitive bis(halomethyloxadiazole) compounds relating to thepresent invention are compounds having structures formed by dimerizinghitherto known photosensitive halomethyloxadiazole compounds. Examplesof known photosensitive halomethyloxadiazole compounds are described,e.g., in U.S. Pat. Nos. 4,212,970, 4,232,106, 4,279,982, and 4,701,399,EP-A-237233, JP-B-03-42462 (the term "JP-B" as used herein means an"examined Japanese Patent Publication"), JP-A-60-138539, JP-A-60-239473,JP-A-60-241049, JP-A-04-328550, JP-A-04-362644, JP-A-05-45875 andJP-A-05-66558. The photosensitive bis(halomethyloxadiazole) compoundsrelating to the present invention include all of the bis compoundsprepared by employing the above described photosensitivehalomethyloxadiazoles as basic mother nuclei and combined with eachother by a certain linkage group.

Of these bis compounds, the compounds represented by one of thefollowing formulae (1) to (4) are preferred: ##STR3## wherein R¹represents --CO--R⁶ --CO--, --C_(n) H_(2n) --, or --C_(n) H_(2n) --R⁷--C_(n) H_(2n) --, n represents an integer of from 1 to 20; R² R³ R¹²and R¹³ are the same or different, and each represents a hydrogen atom,an alkyl group containing 1 to 10 carbon atoms, an alkoxy groupcontaining 1 to 10 carbon atoms, an acyloxy group containing 2 to 10carbon atoms, or a halogen atom; R⁴, R⁵, R¹⁴ and R¹⁵ are the same ordifferent, and each represents a hydrogen atom, an alkyl groupcontaining 1 to 10 carbon atoms, an unsubstituted phenyl group, or asubstituted phenyl group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; X, Y and Z are thesame or different, and each represents a hydrogen atom or a halogenatom, providing that all of X, Y and Z cannot be hydrogen atomssimultaneously; R⁶ represents --C_(m) H_(2m) -- or --OC_(m) H_(2m) O--;m represents an integer of from 2 to 20; R⁷ represents --O--, --S--,--N(R⁸)--, --SO₂ --, --O--SO--O--, --O--CO--R⁹ --CO--O--, --SO₂ R⁹ SO₂--, --CO--R⁹ --CO--, or --O--R¹⁰ --O--; R⁸ represents an alkyl groupcontaining 1 to 10 carbon atom, an unsubstituted phenyl group, or asubstituted phenyl-group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; R⁹ represents --C₁ H₂₁--, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --, --NHC_(k) H_(2k) NH--, --NHC_(k)H_(2k-2) NH--, --NHCH₂ --C₆ H₄ --CH₂ NH--, --OC_(k) H_(2k) O--, or --C₆H₄ --; 1 represents an integer of from 1 to 20; k represents an integerof from 2 to 20; R¹⁰ represents --C_(p) H_(2p) -- or --C_(p) H_(2p)--O--R¹¹ --OC_(p) H_(2p) --; p represents an integer of from 2 to 20;R¹¹ represents --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, --C₆ H₄ --S--C₆ H₄ --,--C₆ H₄ --SO₂ --C₆ H₄ --, --C₆ H₄ --, --C₆ H₄ --O--C₆ H₄ --, --C₆ H₄--C(CF₃)₂ --C₆ H₄ -- or --C₆ H₄ --C₆ H₄ --; and q represents an integerof from 2 to 10.

In general formulae (1) to (4), R¹ is preferably --CO--R⁶ --CO, --C_(n)H_(2n) -- or --C_(n) H_(2n) --R⁷ --C_(n) H_(2n) --, in which nrepresents an integer of from 1 to 12. The formula "--C_(n) H_(2n) --"as used herein includes both straight and branched alkylene groups.

R², R³, R¹² and R¹³ may be the same or different, and each of them ispreferably a hydrogen atom, an alkyl group containing 1 to 5 carbonatoms, an alkoxy group containing 1 to 5 carbon atoms, an acyloxy groupcontaining 2 to 5 carbon atoms, a chlorine atom or a bromine atom.

R⁴, R⁵, R¹⁴ and R¹⁵ may be the same or different, and each of them ispreferably a hydrogen atom, an alkyl group containing 1 to 5 carbonatoms or a phenyl group.

As for the combination of X, Y and Z, CCl₃, CBr₃ or CHCl₂ is preferablein the form of CXYZ.

In general formulae (1) to (4), R⁶ is preferably --C_(m) H_(2m) -- or--OC_(m) H_(2m) O--, in which m represents an integer of from 2 to 12.The formula "--C_(m) H_(2m) --" as used herein includes both straightand branched alkylene groups.

R⁷ is preferably --O--, --S--, --SO₂ --, --O--SO--O--, --O--CO--R⁹--CO--O--, --CO--R⁹ --CO--, or --O--R¹⁰ --O--, and more preferably--O--, --S--, --O--SO--O--, --O--CO--R⁹ --CO--O-- or --CO--R⁹ --CO--.

R⁸ is preferably an alkyl group containing 1 to 8 carbon atoms, anunsubstituted phenyl group or a substituted phenyl group substitutedwith an alkyl or alkoxy group containing 1 to 4 carbon atoms or ahalogen atom.

R⁹ is preferably --C₁ H₂₁ --, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --, --NHC_(k)H_(2k) NH--, --NHC_(k) H_(2k-2) NH--, --OC_(k) H_(2k) O-- or --C₆ H₄ --,in which 1 is an integer of from 1 to 18 and k is an integer of from 2to 12, and more preferably --C₁ H₂₁ --, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --,--NHC_(k) H_(2k) NH--, --NHC_(k) H_(2k-2) NH--, --OC_(k) H_(2k) O--, inwhich 1 is an integer of from 1 to 16 and k is an integer of from 3 to10. The formulae "--C₁ H₂₁ --" and "C_(k) H_(2k) " as used hereininclude both straight and branched alkylene groups.

R¹⁰ is preferably --C_(p) H_(2p) -- or --C_(p) H_(2p) --O--R¹¹ --OC_(p)H_(2p) --, wherein p is an integer of from 2 to 12. The formula "--C_(p)H_(2p) --" as used herein include both straight and branched alkylenegroups.

R¹¹ is preferably --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, in which q is aninteger of from 2 to 6, --C₆ H₄ -- or --C₆ H₄ --O--C₆ H₄ --, and morepreferably --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, in which q is an integerof from 2 to 5. The formula "--C_(q) H_(2q) --" as used herein includeboth straight and branched alkylene groups.

In general formulae (1) to (4), R¹ is particularly preferably--CO--C_(m) H_(2m) --CO--, --C_(n) H_(2n) --, --C_(n) H_(2n)--O--SO--O--C_(n) H_(2n) --, --C_(n) H_(2n) --O--CO--C₁ H₂₁--CO--O--C_(n) H_(2n) --, --C_(n) H_(2n) --O--CO--C₁ H₂₁ O--C₆ H₄--C_(q) H_(2q) --C₆ H₄ --OC₁ H₂₁ --CO--O--C_(n) H_(2n) --, --C_(n)H_(2n) --O--CO--NHC_(k) H_(2k) NH--CO--O--C_(n) H_(2n) --, --C_(n)H_(2n) --O--CO--NHC_(k) H_(2k-2) NH--CO--O--C_(n) H_(2n) --, --C_(n)H_(2n) --CO--OC_(k) H_(2k) O--CO--C_(n) H_(2n) -- and --C_(n) H_(2n)--CO--NHC_(k) H_(2k) NH--CO--C_(n) H_(2n) --, in which m is an integerof from 2 to 10, n is an integer of from 1 to 8, 1 is an integer of from1 to 16, q is an integer of from 3 to 5, and k is an integer of from 3to 10.

Of the compounds represented by general formula (1), compoundsrepresented by the following general formulae (5) to (11) are preferred:##STR4## wherein R¹⁶ is an alkyl group ##STR5## wherein R¹⁷ is an alkylgroup ##STR6## wherein T is a chlorine or bromine atom ##STR7## whereinR¹⁸ is an alkyl group ##STR8## wherein R¹⁹ is an alkyl group ##STR9##

Of the compounds represented by general formula (2), compoundsrepresented by the following general formulae (12) and (13) arepreferred: ##STR10##

Of the compounds represented by general formula (3), compoundsrepresented by the following general formulae (14) and (15) arepreferred: ##STR11##

Of the compounds represented by general formula (4), compoundsrepresented by the following general formulae (16) to (20) arepreferred: ##STR12##

Specific examples of a group represented by R¹ in each of the generalformulae (1) to (4) are described below:

--C₄ H₅ --, --C₅ H₁₀ --, --C₆ H₁₂ --,

--C₃ H₁₆ --, --C₁₀ H₂₀ --, --COC₂ H₄ CO--,

--COC₄ H₈ CO--, --COC₆ H₁₂ CO--,

--C₂ H₄ O--SO--OC₂ H₄ --,

--C₂ H₄ OCOC₂ H₄ COOC₂ H₄ --,

--C₂ H₄ OCOC₄ H₈ COOC₂ H₄ --,

--C₂ H₄ OCOC₆ H₁₂ COOC₂ H₄ --,

--C₂ H₄ OCOC₈ H₁₆ COOC₂ H₄ --,

--C₂ H₄ OCOC₁₆ H₃₂ COOC₂ H₄ --,

--C₃ H₆ OCOC₂ H₄ COOC₃ H₆ --,

--C₃ H₆ OCOC₄ H₈ COOC₃ H₆ --,

--C₃ H₆ OCOC₆ H₁₂ COOC₃ H₆ --,

--C₃ H₆ OCOC₈ H₁₆ COOC₃ H₆ --,

--C₄ H₈ OCOC₂ H₄ COOC₄ H₈ --,

--C₄ H₈ OCOC₄ H₈ COOC₄ H₈ --,

--C₄ H₈ OCOC₆ H₁₂ COOC₄ H₈ --,

--C₄ H₈ OCOC₈ H₁₆ COOC₄ H₈ --,

--C₂ H₄ OCOOC₆ H₁₂ OCOOC₂ H₄ --,

--C₂ H₄ OC₂ H₄ OC₂ H₄ --, --C₂ H₄ OC₂ H₄ --,

--C₃ H₆ OC₃ H₆ --, --C₂ H₄ SC₂ H₄ --,

--C₂ H₄ N(Me)C₂ H₄ --,

--C₃ H₆ COC₂ H₄ COC₃ H₆ --,

--C₂ H₄ SO₂ C₂ H₄ --,

--CH₂ COOC₂ H₄ OCOCH₂ --,

--CH₂ COOC₄ H₈ OCOCH₂ --,

--CH₂ COOC₅ H₁₀ OCOCH₂ --,

--CH₂ COOC₆ H₁₂ OCOCH₂ --,

--CH₂ COOC₈ H₁₆ OCOCH₂ --,

--C₂ H₄ COOC₄ H₈ OCOC₂ H₄ --,

--C₂ H₄ COOC₈ H₁₆ OCOC₂ H₄ --,

--C₃ H₆ COOC₄ H₈ OCOC₃ H₆ --,

--C₃ H₆ COOC₈ H₁₆ OCOC₃ H₆ --,

--CH₂ CONHC₂ H₄ NHCOCH₂ --,

--CH₂ CONHC₄ H₈ NHCOCH₂ --,

--CH₂ CONHC₆ H₁₂ NHCOCH₂ --, ##STR13##

Specific examples of photosensitive bis(halomethyloxadiazole) compoundsof the present invention are described below, wherein the specificexamples are exemplified with lisiting various examples of R¹ (and R⁴and R⁵ in some examples). However, the invention should not be construedas being limited to these examples.

    __________________________________________________________________________     ##STR14##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    1       (CH.sub.2).sub.2                                                      2       (CH.sub.2).sub.3                                                               ##STR15##                                                            4                                                                                      ##STR16##                                                            5       (CH.sub.2).sub.5                                                      6                                                                                      ##STR17##                                                            7                                                                                      ##STR18##                                                            8                                                                                      ##STR19##                                                            9       (CH.sub.2).sub.6                                                      10                                                                                     ##STR20##                                                            11      (CH.sub.2).sub.7                                                      12                                                                                     ##STR21##                                                            13      (CH.sub.2).sub.8                                                      __________________________________________________________________________     ##STR22##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    14                                                                                     ##STR23##                                                            15                                                                                     ##STR24##                                                            16                                                                                     ##STR25##                                                            17                                                                                     ##STR26##                                                            18      (CH.sub.2).sub.9                                                      19      (CH.sub.2).sub.10                                                     20      (CH.sub.2).sub.12                                                     21      (CH.sub.2).sub.16                                                     22      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                     23      C.sub.2 H.sub.4 OC.sub.2 H.sub.4                                      24                                                                                     ##STR27##                                                            25                                                                                     ##STR28##                                                            26      (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 O(CH.sub.2).sub.3                 27      C.sub.2 H.sub.4 OSOOC.sub.2 H.sub.4                                   __________________________________________________________________________     ##STR29##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    28      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.4 COOC.sub.2 H.sub.4                29      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                30      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.10 COOC.sub.2 H.sub.4               31      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.12 COOC.sub.2 H.sub.4               32      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.4 COO(CH.sub.2).sub.3              33      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.3              34      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.8 COO(CH.sub.2).sub.3              35                                                                                     ##STR30##                                                            36                                                                                     ##STR31##                                                            37      (CH.sub.2).sub.4 OCOC.sub.2 H.sub.4 COO(CH.sub.2).sub.4               38      (CH.sub.2).sub.4 OCO(CH.sub.2).sub.4 COO(CH.sub.2).sub.4              39      C.sub.2 H.sub.4 N(Me)C.sub.2 H.sub.4                                  40      C.sub.2 H.sub.4 SO.sub.2 C.sub.2 H.sub.4                              41      C.sub.2 H.sub.4 SO.sub.2 (CH.sub.2).sub.4 SO.sub.2 C.sub.2                    H.sub.4                                                               42      C.sub.2 H.sub.4 OCONH(CH.sub.2).sub.6 NHCOOC.sub.2 H.sub.4            43      C.sub.2 H.sub.4 OCOO(CH.sub.2).sub.6 OCOOC.sub.2 H.sub.4              44      CO(CH.sub.2).sub.4 CO                                                 45      CH.sub.2 COO(CH.sub.2).sub.3 OCOCH.sub.2                              46      CH.sub.2 COO(CH.sub.2).sub.4 OCOCH.sub.2                              47      CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              48      CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              49      CH.sub.2 COO(CH.sub.2).sub.7 OCOCH.sub.2                              50      CH.sub.2 COO(CH.sub.2).sub.8 OCOCH.sub.2                              51      CH.sub.2 COO(CH.sub.2).sub.12 OCOCH.sub.2                             52      (CH.sub.2).sub.3 COO(CH.sub.2).sub.4 OCO(CH.sub.2).sub.3              53      (CH.sub.2).sub.3 COO(CH.sub.2).sub.5 OCO(CH.sub.2).sub.3              54      (CH.sub.2).sub.3 COO(CH.sub.2).sub.6 OCO(CH.sub.2).sub.3              55      CH.sub.2 CONH(CH.sub.2).sub.4 NHCOCH.sub.2                            56      CH.sub.2 CONH(CH.sub.2).sub.6 NHCOCH.sub.2                            57                                                                                     ##STR32##                                                            58                                                                                     ##STR33##                                                            59                                                                                     ##STR34##                                                            60                                                                                     ##STR35##                                                            61                                                                                     ##STR36##                                                            62                                                                                     ##STR37##                                                            171     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.16 COOC.sub.2 H.sub.4               __________________________________________________________________________     ##STR38##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    63      (CH.sub.2).sub.7                                                      64                                                                                     ##STR39##                                                            65      (CH.sub.2).sub.2 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.2              66      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.3              67      CH.sub.2 COO(CH.sub.2).sub.8 OCOCH.sub.2                              __________________________________________________________________________     ##STR40##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    68      (CH.sub.2).sub.6                                                      69                                                                                     ##STR41##                                                            70      (CH.sub.2).sub.2 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.2              71      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.3              72      CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              73      CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              74      CH.sub.2 COO(CH.sub.2).sub.8 OCOCH.sub.2                              __________________________________________________________________________     ##STR42##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    75      (CH.sub.2).sub.5                                                      76                                                                                     ##STR43##                                                            77                                                                                     ##STR44##                                                            78      (CH.sub.2).sub.6                                                      79                                                                                     ##STR45##                                                            80                                                                                     ##STR46##                                                            81      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.4 COOC.sub.2 H.sub.4                82      C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                83      (CH.sub.2).sub.3 OCO(CH.sub.2).sub.4 COO(CH.sub.2).sub.3              84      C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OC.sub.2 H.sub.4                     85      CO(CH.sub.2).sub.3 CO                                                 86      CO(CH.sub.2).sub.4 CO                                                 87      CO(CH.sub.2).sub.5 CO                                                 88      CO(CH.sub.2).sub.6 CO                                                 89      CO(CH.sub.2).sub.8 CO                                                 90      CH.sub.2 COO(CH.sub.2).sub.3 OCOCH.sub.2                              91      CH.sub.2 COO(CH.sub.2).sub.4 OCOCH.sub.2                              92      CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              93      CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR47##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    94      CH.sub.2 COO(CH.sub.2).sub.7 OCOCH.sub.2                              95      CH.sub.2 COO(CH.sub.2).sub.8 OCOCH.sub.2                              96      CH.sub.2 COO(CH.sub.2).sub.12 OCOCH.sub.2                             97      (CH.sub.2).sub.3 COO(CH.sub.2).sub.4 OCO(CH.sub.2).sub.3              98      (CH.sub.2).sub.3 COO(CH.sub.2).sub.5 OCO(CH.sub.2).sub.3              99      (CH.sub.2).sub.3 COO(CH.sub.2).sub.6 OCO(CH.sub.2).sub.3              100                                                                                    ##STR48##                                                            101                                                                                    ##STR49##                                                            102                                                                                    ##STR50##                                                            103                                                                                    ##STR51##                                                            104                                                                                    ##STR52##                                                            105     CH.sub.2 CONH(CH.sub.2).sub.4 NHCOCH.sub.2                            106     CH.sub.2 CONH(CH.sub.2).sub.6 NHCOCH.sub.2                            107                                                                                    ##STR53##                                                            108                                                                                    ##STR54##                                                            __________________________________________________________________________     ##STR55##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    109     (CH.sub.2).sub.5                                                      110     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                111     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR56##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    112     (CH.sub.2).sub.5                                                      113     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.10 COOC.sub.2 H.sub.4               114     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________     ##STR57##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    115     (CH.sub.2).sub.5                                                      116     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.10 COOC.sub.2 H.sub.4               117     CH.sub.2 COO(CH.sub.2).sub.3 OCOCH.sub.2                              __________________________________________________________________________     ##STR58##                                                                    Example Nos.                                                                          R.sup.1                   R.sup.4                                                                           R.sup.5                                 __________________________________________________________________________    118     (CH.sub.2).sub.4          H   Me                                      119     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.3                                                H   Me                                      120     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.4 COOC.sub.2 H.sub.4                                                  H   Ph                                      121     CO(CH.sub.2).sub.8 CO     H   Ph                                      122     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.6 COO(CH.sub.2).sub.3                                                Me  H                                       123     (CH.sub.2).sub.5          Me  H                                       124     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                                                                H   Me                                      __________________________________________________________________________     ##STR59##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    125     (CH.sub.2).sub.5                                                      126     CO(CH.sub.2).sub.4 CO                                                 127     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              128     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR60##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    129     (CH.sub.2).sub.7                                                      130     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                131     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR61##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    132     (CH.sub.2).sub.5                                                      133     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.10 COO(CH.sub.2).sub.3             134     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR62##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    135     (CH.sub.2).sub.5                                                      136     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.12 COOC.sub.2 H.sub.4               137     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________     ##STR63##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    138     (CH.sub.2).sub.5                                                      139     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                140     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR64##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    141     (CH.sub.2).sub.7                                                      142     (CH.sub.2).sub.3 COO(CH.sub.2).sub.4 COO(CH.sub.2).sub.3              143     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________     ##STR65##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    144     (CH.sub.2).sub.5                                                      145     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.12 COOC.sub.2 H.sub.4               146     CH.sub.2 COO(CH.sub.2).sub.3 OCOCH.sub.2                              __________________________________________________________________________     ##STR66##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    147     (CH.sub.2).sub.5                                                      148     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                149     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR67##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    150     (CH.sub.2).sub.7                                                      151     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.4 COO(CH.sub.2).sub.3              152     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________     ##STR68##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    153     (CH.sub.2).sub.5                                                      154     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.12 COOC.sub.2 H.sub.4               155     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR69##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    156     (CH.sub.2).sub.4                                                      157     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.6 COOC.sub.2 H.sub.4                158     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR70##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    159     (CH.sub.2).sub.5                                                      160     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.8 COO(CH.sub.2).sub.3              161     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________     ##STR71##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    162     (CH.sub.2).sub.3                                                      163     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.10 COOC.sub.2 H.sub.4               164     CH.sub.2 COO(CH.sub.2).sub.3 OCOCH.sub.2                              __________________________________________________________________________     ##STR72##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    165     CH.sub.2 CH.sub.2 CHCH.sub.2 CH.sub.2                                         CH.sub.3                                                              166     C.sub.2 H.sub.4 OCO(CH.sub.2).sub.8 COOC.sub.2 H.sub.4                167     CH.sub.2 COO(CH.sub.2).sub.6 OCOCH.sub.2                              __________________________________________________________________________     ##STR73##                                                                    Example Nos.                                                                          R.sup.1                                                               __________________________________________________________________________    168     (CH.sub.2).sub.5                                                      169     (CH.sub.2).sub.3 OCO(CH.sub.2).sub.8 COO(CH.sub.2).sub.3              170     CH.sub.2 COO(CH.sub.2).sub.5 OCOCH.sub.2                              __________________________________________________________________________

When a photosensitive bis(halomethyloxadiazole) compound according tothe present invention contains a double bond in a molecular thereof, itmay be either geometrical isomer. More specifically, substituents on thecarbon atoms forming the double bond may be in the cis or transconformation. However, it is preferable that they are mainly in thetrans conformation. The proportion of the trans conformation to the cisconformation in the compound is preferably in the range of 100:0 to70:30.

The photosensitive bis(halomethyloxadiazole) compounds represented bygeneral formula (1) can be synthesized according to a reaction formula(A), (B) or (C) described below: ##STR74## wherein Q represents ahalogen atom, --OH group, --OL group (wherein L is an releasable group),--COOH group or so on.

Also, the photosensitive bis(halomethyloxadiazole) compounds representedby one of general formulae (2) to (4) can be synthesized according tothe similar reaction.

More specifically, in the reaction formula (A), abis(N-cinnamoyl-N'-haloacetylhydrazine) undergoes a ring closingreaction in a known manner to form a oxadiazole ring therein. In thereaction formulae (B) and (C), on the other hand, a halomethyloxadiazolehaving a reactive group which can react to dimerize is made to reactwith a linkage group-forming agent, thereby obtaining the intended biscompound. The group constituting the linkage part includes, e.g., anether, ester, carbonate and urethane linkage group, and such a linkagecan be easily formed by a known synthesis unit reaction correspondingthereto. The halomethyloxadiazoles which can be used as a startingmaterial can be obtained according to the methods as described, e.g., inU.S. Pat. No. 4,212,970, JP-A-55-24113 and JP-A-02-1884.

The photosensitive bis(halomethyloxadiazole) compounds represented byone of the general formulae (1) to (4) are especially effective whenthey are used as a photoradical polymerization initiator in aphotopolymerizable composition.

When the photosensitive bis(halomethyloxadiazole) compound representedby one of the general formulae (1) to (4) is contained in aphotopolymerizable composition, the photopolymerizable compositionpreferably comprises a polymerizable compound having an ethylenicallyunsaturated bond and a photoradical polymerization initiator, andoptionally a binder, and further a sensitizer, as needed.

Such a photopolymerizable composition is particularly useful for thephotosensitive layer of a photosensitive printing plate, a color proof,a photoresist or so on.

One example of a photosensitive transfer sheet for preparing a colorproof is described below.

The photosensitive transfer sheet of the present invention comprises asupport having thereon a peeling layer and a photopolymerizablephotosensitive resin layer in this order.

As for the material of a support, there can be used a material which ischemically and thermally stable, and has flexibility. The material mayallow permeation of chemical rays therethrough, as needed. Specificexamples of such a material include the various materials described, forexample, in JP-A-47-41830, JP-A-48-9337 and JP-A-51-5101, such ascellulose acetate, polyvinyl chloride, polystyrene, polypropylene and soon. In particular, polyethylene terephthalate, polycarbonate and theheat-treated products thereof are preferred.

On the side of the support opposite the side for forming a peelinglayer, a back layer made of a high molecular substance such as polyvinylbutyral, vinyl chloride-vinyl acetate copolymer, cellulose acetate,etc., may be provided for improving in workability and so on. The backlayer may contain various additives such as a matting agent.

The peeling layer comprising an organic polymer for use in the presentinvention is provided on the support. Materials for the peeling layercan be appropriately selected from those materials which is known asuseful for a peeling layer. Specific examples of such materials includealcohol-soluble polyamides, hydroxystyrene polymers, mixtures ofalcohol-soluble polyamides with hydroxystyrene polymers, polyvinylacetate, poly(meth)acrylates, polyvinyl chloride, polyvinyl butyrate,methylmethacrylate-acrylate copolymers, polyethylene-(meth)acrylic acidcopolymers, cross-linked products of polyethylene-(meth)acrylic acidcopolymers with metals, cellulose acetate butyrate, vinyl chloride-vinylacetate copolymers, cellulose diacetate, cellulose triacetate, polyvinylalcohol, and blends of partially esterified styrene-maleic anhydridecopolymer resins with methoxymethlated nylon. Of these, mixtures ofalcohol-soluble polyamides with hydroxystyrene polymers are preferred.The mixing ratio of an alcohol-soluble polyamide to a hydroxystyrenepolymer in the mixture ranges preferably from 4:6 to 9:1 by weight inview of the releasability from the support under high humidity and theadhesiveness to an image-receiving sheet, another peeling layer, and afinal support in a transfer step.

The peeling layer can be formed by dissolving the above describedmaterial in an appropriate solvent to prepare a coating solution,applying the coating solution to a support, and then drying. Varioussurfactants can be added to the coating solution as an agent forimproving the surface condition. In particular, fluorine-containingsurfactants are effective. The thickness of the peeling layer isgenerally in the range of from 0.1 to 20 μm, preferably in the range offrom 0.2 to 5 μm, and particularly preferably in the range of from 0.3to 3 μm.

Various known materials for photosensitive layers can be used for amaterial of a photopolymerizable photosensitive resin layer provided onthe peeling layer. However, water-or alkali-developablephotopolymerizable photosensitive resins are preferred.

The photopolymerizable photosensitive resin layer is generally comprisesa monomer compound having a boiling point of 150° C. or higher underordinary pressure and capable of forming a photopolymer by at least oneaddition-polymerizable group contained therein, such as a polyfunctionalvinyl monomer or a vinylidene compound; an organic polymer binder; and aphotopolymerization initiator which is activated by actinic rays; andoptionally a thermal polymerization inhibitor. The photopolymerizablephotosensitive resin layer of the present invention is characterized inparticular by the photopolymerization initiator contained therein.

Examples of the vinyl monomer or vinylidene compound which can be usedfor the formation of the photopolymerizable photosensitive resin layerpreferably include unsaturated esters of polyols, and particularlypreferably, acrylic or methacrylic acid esters of polyols. Specificexamples of such unsaturated esters include ethylene glycol diacrylate,glycerol triacrylate, polyacrylate, ethylene glycol dimethacrylate,1,3-propanediol dimethacrylate, polyethylene glycol dimethacrylate,1,2,4-butanetriol trimethacrylate, trimethylolethane triacrylate,pentaerythritol dimethacrylate, pentaerythritol trimethacrylate,pentaerythritol tetramethacrylate, pentaerythritol diacrylate,pentaerythritol triacrylate, pentaerythritol tetraacrylate,dipentaerythritol polyacrylate, 1,3-propanediol diacrylate,1,5-pentanediol dimethacrylate, bisacrylate or bismethacrylate ofpolyethylene glycol having a molecular weight ranging from 200 to 400,and the like.

Unsaturated amides can also be used as the monomer compound. Examplesthereof include unsaturated amides of acrylic or methacrylic acidcontaining an α,ω-diamine, and ethylenebismethacrylamide. Alkylene chainof the unsaturated amide may be linear or branched.

Suitable examples of the organic polymer binder include additionpolymers having a side chain containing carboxylic acid groups, such asmethacrylic acid copolymers (e.g., methylmethacrylate-methacrylic acidcopolymers, ethylmethacrylate-methacrylic acid copolymers,butylmethacrylate-methacrylic acid copolymers,allylmethacrylate-methacrylic acid copolymers, ethylacrylate-methacrylicacid copolymers, ethylmethacrylate-styrene-methacrylic acid terpolymers,benzylmethacrylate-methacrylic acid copolymers, etc.); acrylic acidcopolymers (e.g., ethylacrylate-acrylic acid copolymers,butylacrylate-acrylic acid copolymers, ethylacrylate-styrene-acrylicacid terpolymers, etc.); and, in addition, copolymers of itaconic acid,copolymers of crotonic acid, partially esterified copolymers of maleicacid, and acidic cellulose derivatives having a side chain containing acarboxylic acid group. However, the polymer binder for use in thepresent invention should not be construed as being limited to the abovedescribed examples.

These organic polymer binders may be used alone, or as a mixture of twoor more thereof in an appropriate proportions. Such binders in admixtureshould have good compatibility with one another to the extent that thebinders do not separate during preparing, coating and drying steps ofthe coating composition. The molecular weight of the organic polymerbinders is in a wide range depending on the type of the polymer.However, the weight-average molecular weight is generally in the rangeof 5×10³ to 2×10⁶, and preferably in the range of 1×10⁴ to 1×10⁶.

A proper mixing ratio of the monomer compound to the organic polymerbinder, though it depends on particular combination of the monomercompound and the organic polymer binder, ranges generally from 1:10 to2:1 (by weight).

The photopolymerization initiator contained in the photopolymerizablephotosensitive resin layer is a photopolymerization initiator comprisingat least one photosensitive bis(halomethyloxadiazole) compoundrepresented by one of the foregoing general formula (1), (2), (3) or(4).

In addition to the above described photosensitivebis(halomethyloxadiazole) compounds, other compounds which can initiatethe photopolymerization of compounds containing an ethylenic unsaturatedbond may be used as a photopolymerization initiator in the presentphotopolymerizable photosensitive resin layer. Examples of suchcompounds include the compounds described in Light Sensitive Systemswritten by J. Kosar, chapter 5, such as organic sulfur compounds,peroxides, redox compounds, azo and diazo compounds, substitutedbenzophenone derivatives, aromatic ketones, lophine dimer, and organichalogen compounds other than the present ones.

In the photopolymerizable photosensitive resin layer, thephotopolymerization initiator is preferably contained in an amount of0.01 to 20% by weight, more preferably 0.1 to 15% by weight, based onthe weight of the monomer compounds. The optimum content thereof is inthe range of 0.5 to 10% by weight. When the amount is less than 0.01% byweight, the sufficient sensitivity cannot be obtained; while when it ismore than 20% by weight, whiteness in non-image areas is lowered.Moreover, the amount of the photosensitive bis(halomethyloxadiazole)compound(s) represented by general formula (1), (2), (3) or (4) ispreferably not less than 40% by weight, more preferably not less than50% by weight based on the total weight of the photosensitiveinitiators.

In the photopolymerizable photosensitive resin layer relating to thepresent invention, a reducing agent, e.g., an oxygen scavenger, a chaintransfer agent of active hydrogen donor, and further other compounds topromote a polymerization in a manner of chain transfer reaction can beadditionally used as an assistant agent for accelerating thepolymerization. The oxygen scavenger include phosphine, phosphonates,phosphites, stannous salts and other compounds easily be oxidized byoxygen. Specific examples of such compounds include N-phenylglycine,trimethylbarbituric acid, N,N-dimethyl-2,6-diisopropylaniline, andN,N,N-2,4,6-pentamethylaniline. In addition, thiols, thioketones,trihalomethyl compounds, lophine dimer compounds, iodonium salts,sulfonium salts, azinium salts and organic peroxides are useful as apolymerization accelerator.

The thermal polymerization inhibitor include p-methoxyphenol,hydroquinone, alkyl- or aryl-substituted hydroquinones, t-butylcatechol,pyrogallol, naphthylamine, β-naphthol, phenothiazine, pyridine,nitrobenzene, o-toluquinone and aryl phosphites. However, the thermalpolymerization inhibitor which can be used in the present inventionshould not be construed as being limited to these examples.

The thickness of the photopolymerizable photosensitive resin layer isgenerally in the range of 0.5 to 150 μm, and preferably in the range of1 to 100 μm.

Details of materials and forming methods of the photosensitive resinlayer are described, e.g., in U.S. Pat. Nos. 3,721,557, 3,920,677 and4,482,625, Canadian Patent No. 1,045,872, JP-B-46-35682, JP-A-47-41830,and JP-A-48-93337.

When a coloring substance is used, the coloring substance may becontained in the photopolymerizable photosensitive resin layer, or acoloring layer containing the coloring substance may be providedseparately. The coloring layer may be arranged above or below thephotopolymerizable photosensitive resin layer. However, the coloringlayer is preferably arranged below the photopolymerizable photosensitiveresin layer for obtaining desired sensitivity of the photopolymerizablephotosensitive resin layer in the imagewise exposure step. Examples ofthe coloring substance which can be used include known pigments anddyes. Pigments having a hue equivalent to a color ink (yellow, magenta,cyan and black) can be preferably used for color proofing for printings.Details of coloring pigments and the coloring layer are disclosed, e.g.,in U.S. Pat. No. 4,482,625.

Further, a protective layer is preferably provided on thephotopolymerizable photosensitive resin layer. The protective layer canbe formed by coating a solution of high molecular compound, such aspolyvinyl alcohol, polyvinyl acetate, methyl vinyl ether-maleicanhydride copolymer, polyvinyl pyrrolidone, gelatin, gum arabic, etc.,and then drying the solution.

The photosensitive transfer sheet of the present invention thus preparedcan be used for color proofing, e.g., by undergoing an operationsaccording to a surprint method as described below:

1) A color separation mask is superposed upon a photosensitive transfersheet, and thereto are exposed actinic rays (exposure step).

2) The resulting transfer sheet is processed with a developer to removethe unexposed area, to thereby form a separation image on the peelinglayer (developing step).

3) The above-described steps 1) and 2) are repeated using anotherphotosensitive transfer sheet, to thereby obtain two to four sheets ofcolor proofing sheets having a separation image differently colored.

4) The color proofing sheet having a first color separation image issuperposed upon an image-receiving sheet comprising a support and aphotopolymerizable image-receiving layer so that the color separationimage side may be brought into face-to-face contact with theimage-receiving layer, and subsequently heat and pressure are appliedthereto. Thus, the color proofing sheet is adhered to theimage-receiving sheet in a condition such that the color separationimage is embedded into the uncured image-receiving layer. Then, thesupport of the transfer sheet (temporary support) is removed therefrom,thus finishing the transfer of the image with the peeling layer(transfer step).

Further, each of the remaining color proofing sheets is subjected to thesame operations as described above, wherein each of second and, ifpresent, third and fourth color separation images is transferred intothe same image-receiving sheet in turn so that it may be adjusted to thefirst color separation image. Thus, the image-receiving sheet has fromtwo to four color separation images transferred to the image-receivinglayer in a condition such that all the images are embedded therein.

5) The multicolor image-transferred image-receiving sheet is superposedon a white paper sheet so that the multicolor image may come intocontact with the paper sheet, and then they are subjected to heat andpressure to adhere to each other.

6) The resulting material is subjected to overall exposure to actinicrays from the side of the support of the image-receiving sheet, tothereby photocure the photopolymerizable image-receiving layer.

7) The image having 2 to 4 colors are formed on the white paper bypeeling the support of the image-receiving sheet (temporary support)therefrom. Fine unevenness may be formed on the surface of theimage-receiving layer, as needed, by heating and pressing a mat film,etc. which is superposed onto the image-receiving layer.

Although the support onto which separation image is finally transferredis a white paper sheet in the above description, there can also be usedother supports, such as various kinds of paper sheets, metal sheets,plastic films, glass plates and so on. Also, a multicolor image can bedirectly transferred to the final support without using anyimage-receiving sheet.

The color proofing sheets of from two to four colors which are obtainedin the above described third step can also be used for color proofaccording to a overlay method by directly and precisely superposing thesheets upon one another.

The present invention will be described in detail with reference to thefollowing examples. However, the invention should not be construed asbeing limited to these examples.

EXAMPLE 1

Synthesis of Compound 13:

Bis(N-substituted cinnamoyl-N'-trichloroacetylhydrazine) of formula (D)in an amount of 7.29 g and phosphorus oxychloride in an amount of 9.27 gwere stirred for 2 hours at 105° C. The reaction mixture was poured intoice-cold water, and the precipitated crystals were filtered off, andwashed with methanol and acetone. Thus, 5.21 g of Compound 13 wasobtained m.p. 148°-153° C. ##STR75##

EXAMPLE 2

Synthesis of Compound 29:

Into a solution of 6.99 g of an oxadiazole compound of formula (E) and2.39 g of sebacoyl chloride in 25 ml of acetonitrile, 2.20 g oftriethylamine was dripped as the solution was cooled with ice. Then, theresulting mixture was stirred for 1 hour at room temperature. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized fromacetonitrile. Thus, 7.01 g of Compound 29 was obtained. m.p. 96°-97° C.##STR76##

EXAMPLE 3

Synthesis of Compound 57:

Into a solution of 6.99 g of an oxadiazole compound of formula (E) and3.81 g of 4,4'-isopropylidenediphenoxyacetyl chloride in 25 ml ofacetonitrile, 2.20 g of triethylamine was dripped as the solution wascooled with ice. Then, the resulting mixture was stirred for 1 hour atroom temperature. The reaction mixture obtained was poured into ice-coldwater, and the crystals precipitated was filtered off, andrecrystallized from acetonitrile. Thus, 8.56 g of Compound 57 wasobtained. m.p. 70°-72° C.

EXAMPLE 4

Synthesis of Compound 42:

An oxadiazole compound of formula (E) in an amount of 6.99 g, 1.68 g of1,6-hexamethylenediisocyanate and 0.1 g of dibutyltin diacetate weredissolved in 25 ml of tetrahydrofuran, and stirred for 3 hours at 40° C.The reaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and washed with methanol. Thus,7.75 g of Compound 42 was obtained. m.p. 173°-176° C.

EXAMPLE 5

Synthesis of Compound 27:

Into a solution of 6.99 g of an oxadiazole compound of formula (E) and1.0 g of thionyl chloride in 25 ml of acetonitrile, 2.20 g oftriethylamine was dripped as the solution was cooled with ice. Then, theresulting mixture was stirred for 1 hour at room temperature. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized fromacetonitrile. Thus, 2.84 g of Compound 27 was obtained. m.p. 154° C.

EXAMPLE 6

Synthesis of Compound 171:

Into a solution of 6.99 g of an oxadiazole compound of formula (E) and3.51 g of 1,18-octadecanedionoic acid chloride in 25 ml of acetonitrile,2.20 g of triethylamine was dripped as the solution was cooled with ice.Then, the resulting mixture was stirred for 1 hour at room temperature.The reaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized fromacetonitrile. Thus, 5.96 g of Compound 171 was obtained. m.p. 111°-112°C.

EXAMPLE 7

Synthesis of Compound 62:

An oxadiazole compound of formula (E) in an amount of 6.99 g, 2.80 g ofisophorone diisocyanate and 0.1 g of dibutyltin diacetate were dissolvedin 30 ml of tetrahydrofuran, and stirred for 8 hours at 40° C. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and washed with acetonitrile.Thus, 4.10 g of Compound 62 was obtained. m.p. 180°-183° C.

EXAMPLE 8

Synthesis of Compound 34:

Into a solution of 7.27 g of an oxadiazole compound of formula (F) and2.39 g of sebacoyl chloride in 25 ml of acetonitrile, 2.20 g oftriethylamine was dripped as the solution was cooled with ice. Then, theresulting mixture was stirred for 1 hour at room temperature. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized fromacetonitrile. Thus, 5.27 g of Compound 34 was obtained. m.p. 115°-117°C. ##STR77##

EXAMPLE 9

Synthesis of Compound 5:

Bis(N-substituted cinnamoyl-N'-trichloroacetylhydrazine) of formula (G)in an amount of 14.3 g and phosphorus oxychloride in an amount of 20.2 gwere stirred for 2 hours at 105° C. The reaction mixture was poured intoice-cold water, and the precipitated crystals were filtered off, andwashed with methanol and acetone. Thus, 5.38 g of Compound 5 wasobtained. m.p. 149°-152° C. ##STR78##

EXAMPLE 10

Synthesis of Compound 9:

Bis(N-substituted cinnamoyl-N'-trichloroacetyl-hydrazine) of formula (H)in an amount of 14.6 g and phosphorus oxychloride in the amount of 20.2g were stirred for 2 hours at 105° C. The reaction mixture was pouredinto ice-cold water, and the precipitated crystals were filtered off,and washed with methanol and acetone. Thus, 6.81 g of Compound 9 wasobtained. m.p. 184° C. ##STR79##

EXAMPLE 11

Synthesis of Compound 92:

An oxadiazole compound of formula (I) in an amount of 5.90 g, 1.70 g of1,5-dibromopentane and 1.3 g of sodium hydrogen carbonate were dissolvedin 15 ml of N,N-dimethylacetamide, and stirred for 3 hours at 90° C. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized from an ethylacetate/methanol mixture. Thus, 3.34 g of Compound 92 was obtained. m.p.62°-65° C. ##STR80##

EXAMPLE 12

Synthesis of Compound 93:

An oxadiazole compound of formula (I) in an amount of 9.80 g, 3.05 g of1,6-dibromohexane and 2.2 g of sodium hydrogen carbonate were dissolvedin 25 ml of N,N-dimethylacetamide, and stirred for 3 hours at 90° C. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized from an ethylacetate/methanol mixture. Thus, 7.15 g of Compound 93 was obtained. m.p.109°-112° C.

EXAMPLE 13

Synthesis of Compound 128:

An oxadiazole compound of formula (J) in an amount of 9.80 g, 3.05 g of1,6-dibromohexane and 2.2 g of sodium hydrogen carbonate were dissolvedin 25 ml of N,N-dimethylacetamide, and stirred for 2 hours at 90° C. Thereaction mixture obtained was poured into ice-cold water, and thecrystals precipitated was filtered off, and recrystallized from anacetonitrile/methanol mixture. Thus, 7.01 g of Compound 128 wasobtained. m.p. 123°-126° C. ##STR81##

EXAMPLE 14

To a polyethylene terephthalate film (thickness: 100 μm) as a support, acoating solution having the following composition was applied, and thendried to form a peeling layer having a dry thickness of 0.5 μm.

    ______________________________________                                        [Composition of Coating Solution for Peeling Layer]                           Alcohol-soluble polyamide  5.4     g                                          (CM-8000, trade name, products of Toray                                       Industries, Inc., Viscosity: 23 cps)                                          Polyhydroxystyrene         3.6     g                                          (Resin M, trade name, products of Maruzen Oil                                 Co., Ltd.; Weight-average molecular weight: 5000)                             Methanol                   400     g                                          Methyl cellosolve          100     g                                          ______________________________________                                    

Photosensitive coating solutions of four colors, namely yellow (Y),magenta (M), cyan (C) and black (K), having the following compositionswere respectively prepared as coating solutions for formingphotopolymerizable photosensitive resin layers.

Coating Solution for Photopolymerizable Photosensitive Resin Layers:

    ______________________________________                                        [Composition of Yellow Photosensitive                                         Coating Solution]                                                             Benzylmethacrylate/methacrylic acid                                                                     60      g                                           copolymer (ratio: 73/27 by mole, limiting                                     viscosity number [η]: 0.12)                                               Pentaerythritol tetraacrylate                                                                           43.2    g                                           Photopolymerization initiator (Compound 5)                                                              2.16    g                                           Seika Fast Yellow H-7055  9.4     g                                           (trade name, products of Dainichiseika                                        Colour & Chemicals Mfg. Co., Ltd.)                                            Methylcellosolve acetate  560     g                                           Methyl ethyl ketone       280     g                                           Fluorine-containing surfactant                                                                          1       g                                           (Florade FC-430, trade name, products of                                      Sumitomo 3M Limited)                                                          [Composition of Magenta Photosensitive                                        Coating Solution]                                                             Benzylmethacrylate/methacrylic acid                                                                     60      g                                           copolymer (ratio: 73/27 by mole, limiting                                     viscosity number [η]: 0.12)                                               Pentaerythritol tetraacrylate                                                                           43.2    g                                           Photopolymerization initiator (Compound 5)                                                              2.16    g                                           Seika Fast Carmine 1483   5.2     g                                           (trade name, products of Dainichiseika                                        Colour & Chemicals Mfg. Co., Ltd.)                                            Methylcellosolve acetate  560     g                                           Methyl ethyl ketone       280     g                                           Fluorine-containing surfactant                                                                          1       g                                           (Florade FC-430, trade name, products of                                      Sumitomo 3M Limited)                                                          [Composition of Cyan Photosensitive Coating                                   Solution]                                                                     Benzylmethacrylate/methacrylic acid                                                                     60      g                                           copolymer (ratio: 73/27 by mole, limiting                                     viscosity number [η]: 0.12)                                               Pentaerythritol tetraacrylate                                                                           43.2    g                                           Photopolymerization initiator (Compound 5)                                                              2.16    g                                           Cyanine Blue 4920         5.6     g                                           (trade name, products of Dainichiseika                                        Colour & Chemicals Mfg. Co., Ltd.)                                            Methylcellosolve acetate  560     g                                           Methyl ethyl ketone       280     g                                           Fluorine-containing surfactant                                                                          1       g                                           (Florade FC-430, trade name, products of                                      Sumitomo 3M Limited)                                                          [Composition of Black Photosensitive Coating                                  Solution]                                                                     Benzylmethacrylate/methacrylic acid                                                                     60      g                                           copolymer (ratio: 73/27 by mole, limiting                                     viscosity number [η]: 0.12)                                               Pentaerythritol tetraacrylate                                                                           43.2    g                                           Photopolymerization initiator (Compound 5)                                                              2.16    g                                           Mitsubishi Carbon Black MA-100                                                                          6.6     g                                           (trade name, products of Dainichiseika                                        Colour & Chemicals Mfg. Co., Ltd.)                                            Methylcellosolve acetate  560     g                                           Methyl ethyl ketone       280     g                                           Fluorine-containing surfactant                                                                          1       g                                           (Florade FC-430, trade name, products of                                      Sumitomo 3M Limited)                                                          ______________________________________                                    

The photosensitive coating compositions of these four colors wereapplied to the foregoing four separate support films which were eachhaving the above described peeling layer coated thereon, and dried toform photopolymerizable photosensitive resin layers having the drythickness of 2.4 μm on the respective peeling layers.

Separately, a coating solution having the following composition wasprepared, applied to each of the polymerizable photosensitive resinlayers of the four colors, and dried to form a protective layer having adry thickness of 1.5 μm.

    ______________________________________                                        [Composition of Coating Solution for Protective Layer]                        Polyvinyl alcohol           60     g                                          (GL-05, trade mark, products of The Nippon                                    Synthetic Chemical Industry Co., Ltd.)                                        Water                       970    g                                          Methanol                    30     g                                          ______________________________________                                    

Thus, there were obtained photosensitive transfer sheets of fourdifferent colors (negative working colored photosensitive sheets) eachcomprising a support, a peeling layer, a photopolymerizablephotosensitive resin layer and a protective layer, which were arrangedin this order.

EXAMPLES 15 TO 62

Other 48 sets of photosensitive transfer sheets of four different colorswere prepared in the same manner as in Example 1, except that thephotopolymerization initiator used in the coating solution for formingthe polymerizable photosensitive resin layers was changed from Compound(5) to the same mols of the compound set forth in Table 1, respectively.

                  TABLE 1                                                         ______________________________________                                        Photopolymerization Initiator added                                                  Com-              Com-          Com-                                   Example                                                                              pound    Example  pound  Example                                                                              pound                                  No.    No.      No.      No.    No.    No.                                    ______________________________________                                        15      9       31       71     47     128                                    16     10       32       79     48     129                                    17     13       33       82     49     132                                    18     16       34       86     50     135                                    19     22       35       88     51     139                                    20     27       36       90     52     146                                    21     29       37       92     53     150                                    22     34       38       93     54     152                                    23     42       39       95     55     153                                    24     46       40       99     56     165                                    25     56       41       100    57     167                                    26     57       42       106    58     5 + 82                                 27     58       43       108    59     9 + 82                                 28     61       44       123    60     10 + 79                                29     62       45       125    61     29 + 125                               30     63       46       126    62     61 + 126                               ______________________________________                                    

In each of Examples 58 to 62, the two compounds set forth were mixed inthe same amount (by weight).

EXAMPLE 63

Another set of photosensitive transfer sheets of four different colorswas prepared in the same manner as in Example 14, except that thecomposition of the coating solution for the peeling layer was changed tothe following composition.

    ______________________________________                                        [Coating Solution for Peeling Layer]                                          Alcohol-soluble polyamide 7.2     g                                           (CM-8000, trade name, products of Toray                                       Industries, Inc., Viscosity: 23 cps)                                          Polyhydroxystyrene        1.8     g                                           (Resin M, trade name, products of Maruzen Oil                                 Co., Ltd.; Average molecular weight: 5000)                                    Methanol                  400     g                                           Methyl cellosolve         100     g                                           ______________________________________                                    

EXAMPLES 64 TO 76

Other 13 sets of photosensitive transfer sheets of four different colorswere prepared in the same manner as in Example 63, except that thephotopolymerization initiator used in the coating solution for formingthe polymerizable photosensitive resin layer was changed from Compound(5) to the same mols of the compound set forth in Table 2, respectively.

                  TABLE 2                                                         ______________________________________                                        Photopolymerization Initiator added                                           Example  Compound     Example  Compound                                       No.      No.          No.      No.                                            ______________________________________                                        64        9           71       88                                             65       10           72       90                                             66       29           73       92                                             67       34           74       93                                             68       42           75       95                                             69       61           76       100                                            70       82                                                                   ______________________________________                                    

COMPARATIVE EXAMPLE 1

Still another set of photosensitive transfer sheets of four differentcolors was prepared in the same manner as in Example 14, except that thephotopolymerization initiator used in the coating solution for formingthe polymerizable photosensitive resin layer was changed from Compound(5) to the compound represented by the following formula (K), in whichthe molar amount of the compound used was two times the amount ofCompound (5) in Example 14: ##STR82##

COMPARATIVE EXAMPLE 2

A further set of photosensitive transfer sheets of four different colorswas prepared in the same manner as in Example 14, except that thephotopolymerization initiator used in the coating solution for formingthe polymerizable photosensitive resin layer was changed from Compound(5) to the compound represented by the following formula (L), in whichthe molar amount of the compound used was two times the amount ofCompound (5) in Example 14: ##STR83##

COMPARATIVE EXAMPLE 3

A further set of photosensitive transfer sheets of four different colorswas prepared in the same manner as in Example 63, except that thephotopolymerization initiator used in the coating solution for formingthe polymerizable photosensitive resin layer was changed from Compound(5) to the compound represented by the foregoing formula (K), in whichthe molar amount of the compound used was two times the amount ofCompound (5) in Example 14.

Evaluation of Photosensitive Transfer Sheets

Each set of the photosensitive transfer sheets prepared in Examples andComparative Examples was subjected to a color stain test as describedbelow:

Corresponding color separation masks were superposed upon each of thefour photosensitive transfer sheets having a different color usingregister₋₋ pins. The transfer sheets were imagewise exposed with a 1 kWultra-high pressure mercury lamp, P-607 FW (made by Dainippon ScreenMfg. Co., Ltd.) for 60 seconds, and then processed in an automaticprocessor (Color Art Processor CA-600P, trade name, made by Fuji PhotoFilm Co., Ltd.) at 31° C. for 22 seconds with using a 5-fold dilutedsolution of Color Art Developer CA-1 (trade name, products of Fuji PhotoFilm Co., Ltd.). Thus, for each Example and comparative Example, fourtransfer sheet of different color were obtained which were faithfullyreproduced from the color separation masks.

Separately, a coating solution having the composition described belowwas prepared and applied to a biaxially stretched polyethyleneterephthalate film having a thickness of 100 μm, and was dried to forman image-receiving layer having a dry thickness of 20 μm. Thusimage-receiving sheets was prepared.

    ______________________________________                                        [Composition of Coating Solution for                                          Image-Receiving Layer]                                                        Methylmethacrylate polymer                                                                              90      g                                           (average molecular weight: 100,000, produced                                  by Wako Pure Chemical Industries, Ltd.)                                       Pentaerythritol tetraacrylate                                                                           90      g                                           2,2-Dimethoxy-2-phenylacetophenone                                                                      3.18    g                                           p-Methoxyphenol           0.09    g                                           Methyl ethyl ketone       220     g                                           ______________________________________                                    

Subsequently, a black photosensitive transfer sheet (first color) wasfirst superposed upon the image-receiving sheet so as to bring the imageside of the transfer sheet into contact with the film surface of theimage-receiving material, and the sheets were laminated using a ColorArt Transfer Press, CA-600T (made by Fuji Photo Film Co., Ltd.).Thereafter, the support of the photosensitive transfer sheet was peeled,to thereby transfer a black image into the image-receiving sheet.Further, the three remaining photosensitive transfer sheets each havinga different color were, one by one, positioned and successivelytransferred to the same sheet, to obtained an image-receiving sheethaving a four-colored halftone dot image.

Subsequently, the image-receiving sheet having transferred thereto afour-colored image was superposed upon an art paper sheet (finalsupport), and the sheets were laminated using the above describedtransfer press. Then, the laminated sheet was subjected to overallexposure from the side of the image-receiving sheet with a RoomlightPrinter, P-607 FW (made by Dainippon Screen Mfg. Co., Ltd., equippedwith a 1 kW ultra-high pressure mercury lamp) for 120 seconds.Subsequently, the support of the image-receiving sheet was removed toform a final image on the art paper sheet (color proof).

Non-image areas of the thus obtained color proof having the four-colorhalftone image formed by the foregoing transfer operations was examinedwith a reflection densitometer, RD 918 (made by Macbeth Co., Ltd.,wherein B-filter was used).

Separately, a reference sample was prepared as follows: Theimage-receiving sheet without any transferred images was superposed onan art paper sheet (the same sheet as used above as the final support),and the sheets were laminated using the above described Color ArtTransfer Press (CA-600T, made by Fuji Photo Film Co., Ltd.). Then, thelaminated sheet was subjected to overall exposure from the side of theimage-receiving sheet using a Roomlight Printer, P-607 FW (made byDainippon Screen Mfg. Co., Ltd., equipped with a 1 kW ultra-highpressure mercury lamp) for 120 seconds. Subsequently, the support of theimage-receiving sheet was removed to form an image receiving layer onthe art paper sheet.

The thus obtained reference sample (image-receiving layer having noimage with an art paper sheet) was examined for color stain with areflection densitometer, RD 918 (made by Macbeth Co., Ltd., whereinB-filter was used).

The color stain in the non-image area of each color proof sample wasevaluated by the remainder found by taking the color stain data of thereference sample from the reflection density determined in the non-imagearea of each color proof sample. The evaluation results are shown inTable 3.

                                      TABLE 3                                     __________________________________________________________________________                                 Compara.                                         Example                                                                            Color                                                                             Example                                                                            Color                                                                              Example                                                                            Color                                                                              Example                                                                             Color                                      No.  Stain                                                                             No.  Stain                                                                              No.  Stain                                                                              No.   Stain                                      __________________________________________________________________________    14   0.010                                                                             35   0.010                                                                              56   0.010                                                                              1     0.100                                      15   0.010                                                                             36   0.010                                                                              57   0.010                                                                              2     0.050                                      16   0.010                                                                             37   0.010                                                                              58   0.010                                                                              3     0.090                                      17   0.010                                                                             38   0.010                                                                              59   0.010                                                 18   0.010                                                                             39   0.010                                                                              60   0.010                                                 19   0.010                                                                             40   0.010                                                                              61   0.020                                                 20   0.010                                                                             41   0.010                                                                              62   0.010                                                 21   0.010                                                                             42   0.010                                                                              63   0.010                                                 22   0.010                                                                             43   0.010                                                                              64   0.010                                                 23   0.010                                                                             44   0.020                                                                              65   0.010                                                 24   0.010                                                                             45   0.010                                                                              66   0.010                                                 25   0.010                                                                             46   0.010                                                                              67   0.010                                                 26   0.010                                                                             47   0.010                                                                              68   0.010                                                 27   0.010                                                                             48   0.010                                                                              69   0.010                                                 28   0.010                                                                             49   0.020                                                                              70   0.010                                                 29   0.010                                                                             50   0.020                                                                              71   0.010                                                 30   0.010                                                                             51   0.020                                                                              72   0.010                                                 31   0.010                                                                             52   0.010                                                                              73   0.010                                                 32   0.010                                                                             53   0.010                                                                              74   0.010                                                 33   0.010                                                                             54   0.010                                                                              75   0.010                                                 34   0.010                                                                             55   0.010                                                                              76   0.010                                                 __________________________________________________________________________

As can be seen from Table 3, all of the photosensitive transfer sheetsprepared in accordance with the present invention generates considerablyreduced color stain in their respective non-image areas. Therefore, acolor proof prepared with the photosensitive transfer sheet is excellentwith exhibiting a markedly effect on improvement in similarity ofprinted matters to originals.

Moreover, the photosensitive bis(halomethyloxadiazole) compounds of thepresent invention are novel compounds which can produce free radicalswhen exposed to light, and are useful in the field of recordingmaterials, such as a photosensitive protective films, a printing plate,a photoresist, a color proof and the like.

While the invention has been described in detail and with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A photosensitive bis (halomethyloxadiazole)compound represented by one of the following general formulae (1) to(4): ##STR84## wherein R¹ represents --CO--R⁶ --CO--, --C_(n) H_(2n) --,or --C_(n) H_(2n) --R⁷ --C_(n) H_(2n) --; n represents an integer offrom 1 to 20; R², R³, R¹² and R¹³ are the same or different, and eachrepresents a hydrogen atom, an alkyl group containing 1 to 10 carbonatoms, an alkoxy group containing 1 to 10 carbon atoms, an acyloxy groupcontaining 2 to 10 carbon atoms, or a halogen atom; R⁴, R⁵, R¹⁴ and R¹⁵are the same or different, and each represents a hydrogen atom, an alkylgroup containing 1 to 10 carbon atoms, an unsubstituted phenyl group, ora substituted phenyl group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; X, Y and Z are thesame or different, and each represents a hydrogen atom or a halogenatom, providing that all of X, Y and Z cannot be hydrogen atomssimultaneously; R⁶ represents --C_(m) H_(2m) -- or --OC_(m) H_(2m) O--;m represents an integer of from 2 to 20; R⁷ ; represents --O--, --S--,--N(R⁸)--, --SO₂ --, --O--SO--O--, --O--CO--R⁹ --CO--O--, --SO₂ --R⁹--SO₂ --, --CO--R⁹ --CO--, or --O--R¹⁰ --O--; R⁸ represents an alkylgroup containing 1 to 10 carbon atom, an unsubstituted phenyl group, ora substituted phenyl group substituted with an alkyl or alkoxy groupcontaining 1 to 6 carbon atoms or a halogen atom; R⁹ represents --C₁ H₂₁--, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --, --NHC_(k) H_(2k) NH--, --NHC_(k)H_(2k-2) NH--, --NHCH₂ --C₆ H₄ --CH₂ NH--, --OC_(k) H_(2K) O--, or --C₆H₄ --; 1 represents an integer of from 1 to 20; k represents an integerof from 2 to 20; R¹⁰ represents --C_(p) H_(2p) -- or --C_(p) H_(2p)--O--R¹¹ --OC_(p) H_(2p) --; p represents an integer of from 2 to 20;R¹¹ represents --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, --C₆ H₄ --S--C₆ H₄ --,--C₆ H₄ --SO₂ --C₆ H₄ --, --C₆ H₄ --, --C₆ H₄ --SO₂ --C₆ H₄ --, --C₆ H₄--C(CF₃)₂ --CH₄ -- or --C₆ H₄ --C₆ H₄ --; and q represents an integer offrom 2 to
 10. 2. The photosensitive bis(halomethyloxadiazole) compoundas claimed in claim 1, wherein CXYZ is CCl₃, CBr₃, or CHCl₂.
 3. Thephotosensitive bis(halomethyloxadiazole) compound as claimed in claim 1,wherein R¹ represents --CO--R⁶ --CO--, --C_(n) H_(2n) --, or --C_(n)H_(2n) --R⁷ --C_(n) H_(2n) --; n represents an integer of from 1 to 12;R², R³, R¹² and R¹³ are the same or different, and each represents ahydrogen atom, an alkyl group containing 1 to 5 carbon atoms, an alkoxygroup containing 1 to 5 carbon atoms, an acyloxy group containing 2 to 5carbon atoms, a chlorine atom or a bromine atom; R⁴, R⁵, R¹⁴ and R¹⁵ arethe same or different, and each represents a hydrogen atom, an alkylgroup containing 1 to 5 carbon atoms, or a phenyl group; CXYZ is CCl₃,CBr₃, or CHCl₂ ; R⁶ represents --C_(m) H_(2m) -- or --OC_(m) H_(2m) O--;m represents an integer of from 2 to 12; R⁷ represents --O--, --S--,--SO₂ --, --O--SO--O--, --O--CO--R⁹ --CO--O--, --CO--R⁹ --CO--, or--O--R¹⁰ --O--; R⁹ represents --C₁ H₂₁ --, --C₁ H₂₁ O--R¹¹ --OC₁ H₂₁ --,--NHC_(k) H_(2k) NH--, --NHC_(k) H_(2k-2) NH--, --OC_(k) H_(2k) O--, or--C₆ H₄ --; 1 represents an integer of from 1 to 18; k represents aninteger of from 2 to 12; R¹⁰ represents --C_(p) H_(2p) -- or --C_(p)H_(2p) --O--R¹¹ --OC_(p) H_(2p) --; p represents an integer of from 2 to12; R¹¹ represents --C₆ H₄ --C_(q) H_(2q) --C₆ H₄ --, --C₆ H₄ --, or--C₆ H₄ --O--C₆ H₄ --; and q represents an integer of from 2 to 6.